JPH083524A - Aerosol adhesive composition - Google Patents

Abstract

PURPOSE: To provide the subject composition containing an amorphous polyolefin, being useful for bonding paper, steel sheets, plastic materials, or the like, and packed into a pressure container such as an aerosol can.

CONSTITUTION: There is provided the objective composition containing an amorphous polyolefin (desirably, atactic polypropylene or a copolymer thereof with at least one vinyl monomer). It is desirable that the polyolefin is dissolved or dispersed in a liquefied gas as a propellant (desirably, liquefied petroleum gas, dimethyl ether, or a fluorohydrocarbon) in the absence of an organic solvent.

COPYRIGHT: (C)1996,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aerosol type adhesive composition, and more particularly to an aerosol type adhesive composition containing an amorphous polyolefin as an active ingredient. The pressure-sensitive container such as an aerosol can can be filled with the adhesive composition of the present invention to form an aerosol-type adhesive product. The adhesive composition of the present invention can be advantageously used not only for adhering papers to each other or adhering to steel plates, but also particularly for adhering polyolefin plastic materials such as polyethylene and polypropylene.

[0002]

2. Description of the Related Art Sprayable adhesives (aerosol adhesives) have been developed and provided for convenience of handling. Such adhesives usually contain a base polymer (also called a base polymer), a propellant, an organic solvent and other additives. For example, Japanese Examined Patent Publication No. 45-22239 relates to an aerosol-based adhesive agent based on an elastomer. In this adhesive, a rubber-like elastomer such as styrene-butadiene rubber (SBR) is used as a base polymer, propane, carbon dioxide and fluorohydrocarbon are used as propellants, and hexane, methyl ethyl ketone, methyl isobutyl ketone and various alcohols are used. Is used as an organic solvent. This adhesive is characterized in particular by its high solids content, so that it can be stored for a long period of time and avoids the disadvantages of stringing and spider webs during spraying. You can However, although such an adhesive has good adhesiveness to a porous material such as paper, cardboard, a piece of cloth or Styrofoam, it has an adhesive force to a polyolefin-based plastic material, particularly polypropylene or polyethylene. It has the drawback of being weak.

Japanese Patent Publication No. 46-12640 discloses a sprayable adhesive as described above, which is characterized in that it contains a specific cross-linked acrylate polymer or copolymer in a relatively high concentration. . Using this adhesive, it is possible to perform atomization without the stringing and spider web formation that were the drawbacks of the prior art. However, this adhesive is, like the adhesive described in Japanese Patent Publication No. 45-22239 cited above, good for paper, cardboard, cloth pieces or thin film plastic materials (for example, polyester film). Although it has excellent adhesiveness, it has the drawback of weak adhesion to polyolefin-based plastic materials, particularly polypropylene and polyethylene.

[0004]

Recently, when the aerosol type adhesive is used, the materials to be adhered are diversified, and a strong adhesive force is particularly required for polyolefin plastic materials. Further, from the viewpoint of environmental protection, it is required to provide an aerosol-type adhesive composition that does not use an organic solvent.

Therefore, the present invention firstly provides an aerosol-type adhesive composition which has excellent adhesiveness to polyolefin plastic materials such as polyethylene and polypropylene and which can be uniformly spray-coated. The purpose is to A second object of the present invention is to provide an aerosol-type adhesive composition that does not require the use of an organic solvent and can cope with environmental problems and solvent regulations.

Other objects of the present invention will be readily understood from the following detailed description.

[0007]

According to the present invention, there is provided an aerosol-type adhesive composition containing an amorphous polyolefin. The amorphous polyolefin used as the main active ingredient in the adhesive composition of the present invention has a glass transition temperature (Tg) at room temperature (about 25 ° C.) or lower and can exhibit adhesiveness at room temperature. More specifically, the amorphous polyolefin used in the present invention preferably has a glass transition temperature in the range of -70 to 0 ° C, more preferably -60 to 20 ° C.
The amorphous polyolefin is preferably 0.
4 to 9.0 dl / g, more preferably 0.5 to 6.0 dl / g
g, particularly preferably an intrinsic viscosity (IV) in the range of 0.7 to 3.0 dl / g. Furthermore, the non-crystalline polyolefin is preferably 5,000 to 50,000,
000, particularly preferably 50,000 to 5,000,0
Having a weight average molecular weight in the range of 00.

The non-crystalline polyolefin used in the present invention includes various non-crystalline olefin polymers and copolymers such as polyolefin or a copolymer of olefin and one or more vinyl monomers. The polyolefin used is preferably atactic polypropylene or atactic polypropylene and one or more vinyl monomers such as maleic acid,
Copolymers with 1-butene, etc., and α-olefins having 4 to 16 carbon atoms, such as 1-butene, 1-pentene, 1
-Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-
Tridecene, 1-tetradecene, 1-pentadecene, 1
A homopolymer or copolymer such as hexadecene.
These polymers and copolymers may be used alone, or two or more kinds may be mixed and used.

The α-olefin homopolymers or copolymers that can be used in the practice of the present invention include a wide variety of polymers and copolymers, as described above. Now, a preferred example of a useful poly-α-olefin can be represented by the following formula:

[0010]

Embedded image

(In the above formula, R ₁ and R ₂ may be the same or different and each represents a monovalent hydrocarbon group having 4 to 8 carbon atoms, and x and y are respectively described. Is a mole% of the monomer, and x is preferably
50-100 mol%).

Further, some examples of the non-crystalline polyolefins which are useful in the present invention and which are commercially available are atactic polypropylene (available from Lexen Products under the product number "RT2304"), atactic Copolymer of polypropylene and maleic acid (Product number "P1824" from Lexen Products Ltd.)
-012 "). Further, polybutene, polyhexene, polyoctene, polydecene, polydodecene, and copolymers thereof are also available with various intrinsic viscosities.

In the aerosol type adhesive composition of the present invention, the non-crystalline polyolefin is used as one of the active ingredients of the adhesive. Here, the term "adhesive active ingredient" means a component that functions as an adhesive in an aerosol-type adhesive composition (in other words, a component that can directly participate in the adhesive action), and therefore, for injection. Volatile components such as liquefied gases and organic solvents are excluded from the scope of this term.
In a preferred embodiment of the invention, the adhesive active ingredient comprises i) a base polymer comprising an amorphous polyolefin, or ii) a base polymer comprising an amorphous polyolefin, and an adhesive It consists of an imparting agent.

A base polymer comprising an amorphous polyolefin means that the base polymer consists solely of the amorphous polyolefin or a mixture of the amorphous polyolefin and one or more other base polymers. Means to become. Preferred examples of "other base polymers" include styrene-based copolymers such as styrene-butadiene block copolymers, acrylic-based copolymers such as acrylate ester copolymers, acrylonitrile rubber, natural rubber, and chloroprene. , Ethylene-vinyl acetate copolymer (EVA), silicone-based copolymer and the like. Particularly preferably, a styrene-based copolymer such as a styrene-butadiene block copolymer can be used. The styrene-butadiene block copolymer is available, for example, from Phillips Petroleum under the trade name "Solprene 411P". When the amorphous polyolefin is used in combination with other base polymer as described above, the mixing ratio of the two is
It is preferable that 100 to 10,000 parts by weight of the other base polymer is mixed with 100 parts by weight of the amorphous polyolefin.

As used herein, the terms "base polymer" and "tackifier" are used in their respective generally accepted meanings in the art, with the former being The main component of the adhesive is the base polymer for exerting the cohesive strength of the adhesive itself, and the latter is combined with the base polymer to improve the interfacial adhesion of the adhesive. It means a resin material.

The tackifier that can be advantageously used in combination with the base polymer, if necessary, can be arbitrarily selected from those generally used in this technical field. Examples of the tackifier useful in the present invention include natural resins such as rosin and its derivatives (rosin ester) and terpene resins,
Further, a synthetic resin such as a petroleum resin can be used. Rosin is a refined resin acid contained in pine, contains abietic acid as a main component, and contains about 70
It has a softening point of ~ 80 ° C. Rosin is available as "rosin" from Arakawa Chemical Industries, Ltd., for example.
The rosin ester is obtained by esterifying rosin with alcohol, glycerin or the like, preferably 70 to 100 ° C.
Has a softening point of. Rosin ester is commercially available, for example, from Arakawa Chemical Industry Co., Ltd. under the trade name "Super Ester A10.
0 "and the product name" Stevelite Ester 10 "from Rika Hercules Co., Ltd., respectively. The terpene-based resin includes a terpene-based polymer such as pinene and limonene, preferably 55 to 135.
It has a softening point of ° C. This type of resin is commercially available, for example, from Rika Hercules Co., Ltd. under the trade name "Piccolite".
lyte) A115 ”and“ Picolite A135 ”
In addition, the product name "Zona Letts (Z
onarez) 7115 ", respectively.
The petroleum-based resin is typically a hydrocarbon resin having 5 to 9 carbon atoms, and preferably has a softening point of 80 to 145 ° C. The "softening point" described above is a ball-and-ring softening point (according to JIS K2207). This type of hydrocarbon resin is commercially available, for example, from Arakawa Chemical Industry Co., Ltd. under the trade name "ALCON P-90".
In addition, product names “Regalrez 1078” and “Rigalets 1126” from Rika Hercules Co., Ltd.
, Respectively, are available.

The aerosol type adhesive composition of the present invention contains a liquefied gas for injection as a propellant. The liquefied gas for injection is to inject an adhesive active ingredient containing an amorphous polyolefin from a pressure resistant container such as an aerosol can,
It is a gas liquefied by pressurization. Such liquefied gas is preferably liquefied petroleum gas such as propane, n-butane, isobutane, dimethyl ether, Freon 134a.
(CH ₂ FCF ₃ ), fluorocarbons such as Freon 152a (CH ₃ CHF ₂ ), and mixtures thereof.

The adhesive active ingredient is dissolved or dispersed in the liquefied gas for injection in the presence or absence of an organic solvent. Where "dissolve" or "disperse"
The term means that the polyolefin may be contained in the liquefied gas in any form. When an organic solvent is used in the present invention, suitable organic solvents include those generally used in this technical field, for example, aliphatic hydrocarbon solvents such as n-pentane and n-hexane. it can.

It is noteworthy in the present invention that the adhesive active ingredient containing the amorphous polyolefin can be dissolved or dispersed in the liquefied gas for injection without using an organic solvent. In this case, the liquefied gas for injection has a function as a solvent in addition to a function as a propellant, and as described above, preferably, liquefied petroleum gas, dimethyl ether, fluorohydrocarbon and these Selected from the group consisting of mixtures.

In the aerosol type adhesive composition of the present invention, the base polymer, the liquefied gas for injection, the tackifier and the organic solvent are each used for the purpose intended for the adhesive composition,
It can be mixed in various ratios depending on the desired effect, the conditions of adhesion, the material to be adhered, and other factors. The liquefied gas for injection is 100 to 3,500 parts by weight with respect to 100 parts by weight of the base polymer (about 3 to 3 in solid content concentration).
It is preferable to blend in the range of 25%), and the optimum blending amount is determined in consideration of the solid content concentration and the like. The amount of liquefied gas is 1
If the amount is less than 100 parts by weight, the viscosity of the resulting composition becomes high, and therefore the spray shape is "particulate" (when the polymer is in a dispersed state) or "race-like" (when the polymer is (When it is in a dissolved state).
If the shape of the spray does not become "particulate" or "lace", it becomes difficult to uniformly spray the adhesive composition over a wide range. On the other hand, if the amount of liquefied gas exceeds 3,500 parts by weight, the active ingredient of the adhesive becomes diluted (solid content concentration is about 3% or less), so the number of injections must be increased to obtain high adhesive strength. I have to. The liquefied gas for injection is 500 to 3,2 with respect to 100 parts by weight of the base polymer.
It is particularly preferable to blend in the range of 00 parts by weight.

The tackifier is preferably added in an amount of 0 to 200 parts by weight based on 100 parts by weight of the base polymer. That is, the tackifier need not be compounded, and if it is compounded, it is preferably 200 parts by weight or less in order to avoid the tendency of the adhesive strength to decrease. The tackifier is 50 to 1 with respect to 100 parts by weight of the base polymer.
It is particularly preferable to blend in the range of 00 parts by weight.

The organic solvent is preferably blended in the range of 0 to 2,000 parts by weight with respect to 100 parts by weight of the base polymer. That is, the organic solvent may not be blended for the purpose of preventing environmental pollution, and it is particularly preferable to use the solvent-free type as such. The organic solvent, if incorporated, is preferably 2,000 parts by weight or less. This is because when the amount of the organic solvent exceeds 2,000 parts by weight, it takes a long time from the completion of the spray coating to the development of the adhesive force, because the sprayed composition dries slowly. This is because, as in the case of the liquefied gas, the active ingredient of the adhesive becomes diluted, so that the number of injections must be increased in order to obtain a high adhesive force. When the organic solvent is added, it is particularly preferable that the amount of the organic solvent be 900 parts by weight or less based on 100 parts by weight of the base polymer.

The aerosol type adhesive composition of the present invention is used by filling it into a pressure vessel such as an aerosol can made of metal such as steel or a glass bottle. Such a pressure vessel can have any shape and size, and
If necessary, in order to prevent undesired reactions and the like from occurring between the inner wall of the container and the adhesive composition, the inner wall of the container may be coated with a suitable material.
Suitable coating materials can include, for example, epoxy resins.

[0024]

The aerosol type adhesive composition of the present invention contains a non-crystalline polyolefin as a main active ingredient. According to the present invention, as described above, it is possible to obtain an excellent adhesive force particularly to a polyolefin-based plastic material, but the exact reason for this has not yet been clarified, but the adhesive is effective. It is speculated that the fact that the polyolefin in the component and the polyolefin of the material to be bonded have a chemically similar structure, and thus a strong bond which has never existed is developed between them, is presumed to be involved. Also, noteworthy, this excellent adhesive strength is effective for paper and steel plate as well.

The non-crystalline polyolefin is also used as a liquefied gas for injection in an aerosol type adhesive composition and can be completely dissolved or dispersed in propane, butane, isobutane, dimethyl ether and the like, which have relatively low toxicity. The use of such a liquefied gas makes it possible to provide a solventless type product in which organic solvents which may be a source of environmental pollution are excluded. In addition, since these liquefied gases can be evaporated very quickly, the drying of the adhesive can be completed in an extremely short time.

[0026]

EXAMPLES Next, the present invention will be described in detail with reference to the following examples and comparative examples. In the following, the amounts of the constituent components of the composition are shown in parts, but this means “parts by weight” unless otherwise specified. Example 1 In this example, an aerosol-type adhesive composition containing the following components in the amounts described was prepared.

Base polymer Atactic polypropylene / maleic acid copolymer (P1824-012 manufactured by Lexen) 5 parts Organic solvent None Spraying liquefied gas Dimethyl ether 95 parts Tackifier None Base polymer is put in an aerosol can and aerosolized. The valve was crimped and the can was sealed. Next, dimethyl ether (hereinafter referred to as DME) is filled in an aerosol can,
After being sufficiently shaken by hand, the desired aerosol-type adhesive composition was obtained.

In order to evaluate the adhesive strength of the obtained aerosol type adhesive composition, the peel adhesion strength of polypropylene (PP) plate to polyester (PET) film, paper to paper and cotton canvas to steel plate is specified in JIS K6854. The measurement was performed according to the test method described above. The PP plate used in the test in this example has a thickness of 2.0 mm, the PET film has a thickness of 0.1 mm, the cotton canvas is a normal cotton canvas 1209 specified in JIS L3102, and the steel plate is a cold specified JIS G3141. It was a rolled steel plate (plate thickness 0.8 mm).

In the adhesive strength test of PP plate / PET film and cotton canvas / steel plate, the surface of each material to be adhered was
The adhesive was spray-applied four times at intervals of 20 cm. After standing for 5 to 10 seconds, the two materials to be bonded were bonded together. The bonded portion was crimped by a metal roller (5 kg) for 6 reciprocations. After standing in an oven at 60 ° C. for 24 hours, the temperature was returned to room temperature, and then a peeling test was conducted with a tensile tester at a pulling speed of 200 mm / min.

In the paper-to-paper adhesive strength test, the adhesive was spray-applied once and twice on one surface of the high-quality paper at intervals of 20 cm. After being left for 5 to 10 seconds, a high-quality paper not coated with the adhesive was attached to the high-quality paper having the adhesive-coated surface. The bonded part was rolled with a rubber roller (2 kg) twice. After being left at room temperature for 24 hours, a peel test was conducted with a tensile tester at a tensile speed of 300 mm / min.

The results of the peel test are shown below. Bonding the material to peel strength (g / 25 mm) PP plate / PET film 700 Paper / Paper single coat 240 2 coats - (torn paper) The cotton canvas / steel 5000, the adhesive compositions obtained cans In order to evaluate the state (dissolution-dispersion) inside, the above method was repeated using a glass pressure bottle instead of the aerosol can. It was visually confirmed that the composition was completely dissolved in the pressure bottle. Furthermore, the shape of the spray obtained by using this adhesive composition was a lace shape, and no scattering to the peripheral part was observed. Example 2 Preparation 1: The procedure described in Example 1 above was repeated. However, in the case of this example, the same amount (5 parts) of polyhexene (intrinsic viscosity, IV = 0.8) was used as the base polymer instead of the polypropylene / maleic acid copolymer, and the same amount was used instead of DME. Amount (95 parts) of propane was used. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25mm) PP plate / PET film 1100 Paper / paper 1 time coating 280 2 times coating 980 Cotton canvas / steel sheet-Dissolution state in can: Complete dissolution Spray shape Race 2 Preparation 2: The above Preparation 1 was repeated by changing the amounts of polyhexene and propane used to measure the peel adhesion strength of the PP plate / PET film and to evaluate the dissolved state in the can and the shape of the spray. The following results were obtained (for reference, the results of Preparation 1 are also shown).

Polyhexene propane dissolved state Spray shape Peeling adhesion strength 15 parts 85 parts Complete dissolution lace-like 1200 5 parts 95 parts Complete dissolution lace-like 1100 3 parts 97 parts Complete dissolution lace-like 700 Peeling adhesion strength = g / 25 mm Preparation 3: The amount of polyhexene used in Preparation 1 was changed (the amount of propane was the same), and Alcon P- was used as a tackifier.
90 (petroleum-based hydrocarbon resin available from Arakawa Chemical Industry Co., Ltd.) was used together and repeated to measure the peel adhesion strength of the PP plate / PET film and to evaluate the dissolved state in the can and the shape of the spray. . The following results were obtained (for reference, the results of Preparation 1 are also shown).

Polyhexene Alcon P-90 Dissolved Spray Form Peeling Adhesive Strength 5 parts 0 parts Complete Melting Lace 1100 3 parts 2 parts Complete Melting Lace 1800 2 parts 3 parts Complete Melting Lace 1500 peel adhesion strength = g / 25 mm Preparation 4: The above Preparation 1 was repeated by changing the amounts of polyhexene and propane used together with n-hexane as an organic solvent to measure the peel adhesion strength of the PP plate / PET film and dissolve it in the can. The condition and spray shape were evaluated. The following results were obtained (for reference, the results of Preparation 1 are also shown). Polyhexene propane Organic solvent Dissolved state Spray shape Peeling adhesive strength 5 parts 95 parts 0 parts Complete dissolution lace 1100 5 parts 40 parts 55 parts Complete dissolution lace 1200 3 parts 37 parts 60 parts Complete dissolution lace 600 peel adhesion strength = G / 25 mm

Example 3 The procedure described in Example 1 above was repeated. However, in this example, the same amount of polyoctene (intrinsic viscosity, IV =
0.8) was used and the same amount of propane was used instead of DME. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25mm) PP plate / PET film 1000 Paper / paper 1 time coating 170 2 times coating 490 Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray shape : Lace shape

Example 4 The procedure described in Example 1 above was repeated. However, in the case of this example, the same amount of polyoctene / polydecene copolymer was used as the base polymer instead of the polypropylene / maleic acid copolymer, and the same amount of propane was used instead of DME. The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25mm) PP plate / PET film 900 Paper / paper 1 time coating 220 2 times coating 880 Cotton canvas / steel sheet-Dissolution state in can: Complete dissolution Spray shape : Lace shape

Example 5 The procedure described in Example 1 above was repeated. However, in the case of this example, the amount of the polypropylene / maleic acid copolymer used as the base polymer was changed to 3 parts, and in order to compensate for the decrease in the base polymer, a tackifier (from Arakawa Chemical Industry Co., Ltd. 2 parts of petroleum-based hydrocarbon resin available as "Arcon P-90" was used. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25mm) PP board / PET film 1200 Paper / paper 1 time coating- (breaking paper) 2 times coating- (breaking paper) Cotton canvas / steel sheet 1800 cans Dissolved state inside: Completely dissolved Spray form: Lace

Example 6 The procedure described in Example 5 above was repeated. However, in this example, the same amount of atactic polypropylene (available from Lexen as "RT2304") was used as the base polymer instead of the polypropylene / maleic acid copolymer. The results obtained are shown below. Peel adhesion strength: Adhesive target material Peel adhesion strength (g / 25mm) PP board / PET film 200 Paper / paper 1 time application 140 2 times application 250 Cotton canvas / steel sheet 900 Dissolved in can: Dispersion Spray shape: Particulate

Example 7 The procedure described in Example 5 above was repeated. However, in the case of this example, instead of the polypropylene / maleic acid copolymer as the base polymer, the same amount of polyhexene (intrinsic viscosity, IV =
0.8) was used and the same amount of propane was used instead of DME. The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25mm) PP plate / PET film 1800 Paper / paper 1 time coating 220 2 times coating- (paper tear) Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray form: lace

Example 8 The procedure described in Example 1 above was repeated. However, in the case of this example, the amount of DME used was changed to 55 parts, and instead, 40 parts of n-hexane as an organic solvent was used. The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25 mm) PP plate / PET film 800 Paper / paper 1 time coating 300 2 times coating- (paper tear) Cotton canvas / steel sheet 4600 Melting state in can: Complete dissolution Spray form: lace

Example 9 The procedure described in Example 8 above was repeated. However, in the case of this example, instead of the polypropylene / maleic acid copolymer as the base polymer, the same amount of polyhexene (intrinsic viscosity, IV =
0.8) was used, 40 parts of propane was used instead of DME, and 55 parts of n-hexane as an organic solvent was further used. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25mm) PP board / PET film 1200 Paper / Paper once coating 200 Double coating 700 Cotton canvas / Steel plate-Dissolved state in can: Complete dissolution Spray shape : Lace shape

Example 10 The procedure described in Example 8 above was repeated. However, in this example, the same amount of polyoctene (intrinsic viscosity, IV =
0.8) was used, 40 parts of propane was used instead of DME, and further 55 parts of n-pentane as an organic solvent was used. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25mm) PP plate / PET film 1000 Paper / Paper 1 time coating 200 2 times coating 550 Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray shape : Lace shape

Example 11 (Comparative Example) The procedure described in Example 8 above was repeated. However, in the case of this example, polypropylene / polypropylene was used as the base polymer for comparison.
A 6 part acrylic rubber (partially crosslinked acrylic acid ester copolymer available as "RD-984" from US 3M Company) was used in place of the maleic acid copolymer, and the DME was 40%.
Part was used instead, and 54 parts of n-hexane as an organic solvent was used. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25 mm) PP plate / PET film 80 Paper / paper 1 time coating 40 2 times coating 90 Cotton canvas / steel sheet-Dissolved state in can: Dispersion Spray shape: Particulate

Example 12 (Comparative Example) The procedure described in Example 8 above was repeated. However, in the case of this example, polypropylene / polypropylene was used as the base polymer for comparison.
Using 4 parts of styrene-butadiene block copolymer (available as "Sorprene 411P" from Philips Petroleum) in place of the maleic acid copolymer,
DME was changed to 50 parts and used, and further 46 parts of toluene as an organic solvent was used. The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25mm) PP plate / PET film 0 Paper / Paper 1 time coating 2 times 0 Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray shape : Lace shape

Example 13 The procedure described in Example 2 above was repeated. However, in the case of this example, the amount of polyhexene (intrinsic viscosity, IV = 0.8) was changed to 3 parts, and the amount of propane was changed to 40 parts,
Further, using 55 parts of n-hexane as an organic solvent,
In addition, 2 parts of a tackifier (petroleum hydrocarbon resin available as "Alcon P-90" from Arakawa Chemical Industry Co., Ltd.) was used to compensate for the decrease in the base polymer. The results obtained are shown below. Peeling adhesion strength: Peeling adhesion strength of the material to be bonded (g / 25 mm) PP plate / PET film 2300 Paper / paper 1 time coating 310 2 times coating- (breaking paper) Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray form: lace

Example 14 The procedure described in Example 13 above was repeated. However, in the case of this example, the same amount of polyoctene (intrinsic viscosity, IV = 0.8) was used as the base polymer instead of polyhexene. The results obtained are shown below. Peeling adhesion strength: Adhesion target material Peeling adhesion strength (g / 25 mm) PP plate / PET film 2000 Paper / paper 1 time coating 280 2 times coating- (breaking paper) Cotton canvas / steel sheet-Dissolved state in can: Complete dissolution Spray form: lace

Example 15 (Comparative Example) The procedure described in Example 11 (Comparative Example) was repeated. However, in the case of this example, 50% of n-hexane as an organic solvent is used.
The terpene resin (Pikalite A11 from Rika Hercules Co., Ltd. is used as a tackifier.
5 ") (available as" 5 "). The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25mm) PP board / PET film 110 Paper / paper 1 time coating 110 2 times coating 200 Cotton canvas / steel sheet 1200 Dissolved state in can: Dispersion Spray shape: Particulate

Example 16 (Comparative Example) The procedure described in Example 12 (Comparative Example) was repeated. However, in the case of this example, toluene as an organic solvent was changed to 42 parts, and further, as a tackifier, a terpene resin (“Picolite A135” from Rika Hercules Co., Ltd.) was used.
4 parts). The results obtained are shown below. Peel adhesion strength: Adhesion target material Peel adhesion strength (g / 25mm) PP board / PET film 160 Paper / paper 1 time coating- (breaking paper) 2 times coating- (breaking paper) Cotton canvas / steel sheet 3500 cans Dissolved state inside: Completely dissolved Spray form: Lace

Example 17 The procedure described in Example 2 above was repeated. However, in the case of this example, the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 18 The procedure described in Example 2 above was repeated. However, in the case of this example, instead of propane as the liquefied gas for injection, the same amount of n
-Butane was used. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 19 The procedure described in Example 2 above was repeated. However, in the case of this example, instead of propane as the liquefied gas for injection, the same amount of D
ME was used. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 20 The procedure described in Example 2 above was repeated. However, in the case of this example, polyhexene (intrinsic viscosity, I
V = 0.8) instead of the same amount of polyhexene (intrinsic viscosity,
IV = 1.6) and the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 21 The procedure described in Example 2 above was repeated. However, in the case of this example, polyhexene (intrinsic viscosity, I
V = 0.8) instead of the same amount of polyhexene (intrinsic viscosity,
IV = 1.8) and the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 22 The procedure described in Example 3 above was repeated. However, in the case of this example, the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 23 The procedure described in Example 3 above was repeated. However, in the case of this example, instead of propane as the liquefied gas for injection, the same amount of n
-Butane was used. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 24 The procedure described in Example 3 above was repeated. However, in the case of this example, instead of propane as the liquefied gas for injection, the same amount of D
ME was used. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 25 The procedure described in Example 3 above was repeated. However, in the case of this example, polyoctene (intrinsic viscosity, I
V = 0.8) instead of the same amount of polyoctene (intrinsic viscosity,
IV = 2.0) and the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 26 The procedure described in Example 3 above was repeated. However, in the case of this example, polyoctene (intrinsic viscosity, I
V = 0.8) instead of the same amount of polyoctene (intrinsic viscosity,
IV = 2.8) was used and the same amount of isobutane was used instead of propane as the liquefied gas for injection. The state (dissolution-dispersion) in the can of the obtained adhesive composition was evaluated using a glass pressure bottle, and it was possible to visually confirm that the composition was in a completely dissolved state in the pressure bottle. . The shape of the spray obtained by using this adhesive was lace-like, and no scattering to the peripheral part was observed.

Example 27 The procedure described in Example 2 above was repeated. However, in the case of this example, the composition of the adhesive composition filled in the aerosol can was changed as follows.

Base polymer Polyhexene (intrinsic viscosity, IV = 0.8) 0.4 part Styrene-butadiene block copolymer (Sorprene 411P manufactured by Phillips Petroleum Co., Ltd.) 4 parts Organic solvent Toluene 41.6 parts Liquefaction for injection Gas dimethyl ether 50 parts Tackifier terpene resin 4 parts (Ricoh Hercules Picolite A135) When the adhesive strength of the obtained aerosol type adhesive composition was evaluated with respect to the PP plate to PET film, the peel adhesion strength was found to be It was 1100 g / 25 mm.

[0060]

As described above, according to the present invention,
For a wide range of materials to be adhered, from thin materials such as paper and film to steel sheets, and especially, for example, polyethylene,
It is possible to provide an aerosol-type adhesive that exhibits good adhesion to a polyolefin plastic material such as polypropylene. Further, in the present invention, the degree of adhesive strength to these various materials can be arbitrarily controlled by changing the composition and formulation of the adhesive composition. For example, in the case of adhesive strength to paper, it is possible to make it possible to peel the paper once attached without peeling it, or to make strong adhesion so that the paper can be torn.

Further, the adhesive composition of the present invention can exhibit a uniform dissolved or dispersed state in the aerosol container, so that when the composition is sprayed from the container, the nozzle is not clogged. There is no blurring.
Whether the composition is in a dissolved state or in a dispersed state can be controlled by selecting the base polymer used in the composition. Patterns up to the pattern (dispersed state) can be obtained at any stage. in addition,
The spray is extremely scattered, and the effect of not contaminating the surrounding area can be obtained.

Furthermore, according to the present invention, it is possible to produce an aerosol type adhesive containing no organic solvent,
Therefore, environmental pollution and harm to the human body can be avoided, and the drying of the adhesive can be significantly shortened because no solvent is used. In this case, the liquefied gas is also used as a solvent, but since the liquefied gas has a relatively low toxicity, it is possible to obtain an effect of significantly reducing the influence on human health.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinji Sugii 3-8-8 Minamihashimoto, Sagamihara-shi, Kanagawa Sumitomo 3M Limited

Claims (5)

[Claims] 1. An aerosol type adhesive composition containing an amorphous polyolefin. 2. The polyolefin is atactic
The aerosol-type adhesive composition according to claim 1, which is polypropylene or a copolymer of atactic polypropylene and one or more vinyl monomers. 3. The polyolefin has 4 to 16 carbon atoms.
The aerosol-type adhesive composition according to claim 1, which is a homopolymer or copolymer of the α-olefin. 4. The aerosol-type adhesive composition according to any one of claims 1 to 3, wherein the polyolefin is dissolved or dispersed in a liquefied gas for injection in the absence of an organic solvent. . 5. The aerosol-type adhesive composition according to claim 4, wherein the liquefied gas is selected from the group consisting of liquefied petroleum gas, dimethyl ether, fluorocarbons and mixtures thereof.